Unsaturated fatty alcohols and method of preparing them

ABSTRACT

New unsaturated fatty alcohols of the formula: ##STR1## in which n=2 or 4 are provided and are prepared by the novel process of reacting butadiene with water in the presence of a palladium salt and orthoboric acid, B(OH) 3 , in a polar aprotic solvent.

The present invention relates to new unsaturated fatty alcohols and to anovel process for preparing them.

It is an object of the present invention to provide novel unsaturatedfatty alcohols.

It is a further object to provide a novel process of preparing the novelunsaturated fatty alcohols of the invention.

Further objects will be apparent to those skilled in the art from thepresent description.

GENERAL DESCRIPTION OF THE INVENTION

The compounds of the invention have the general formula ("A") shownbelow: ##STR2## in which n is equal to 2 or 4.

The invention therefore concerns more particularly the novel compounds:hexadeca-1,6,10,15-tetraen-3-ol (n=2) andtetracosa-1,6,10,14,18,23-hexaen-3-ol (n=4).

The invention also has as its object a process of preparing compounds offormula "A" comprising reacting butadiene with water in the presence ofa palladium salt and orthoboric acid, B(OH)₃, in a polar aproticsolvent.

In accordance with one particular embodiment of the process of theinvention, a carboxylic acid is present in the polar aprotic solventsimultaneously with the palladium salt and the orthoboric acid.

It should be emphasized that, within the present invention, the additionof and presence of carboxylic acid is not necessary. However, it makesit possible to increase the stability of the catalytic system formedfrom the palladium salt. It also makes it possible to increase theselectivity for the alcohol of the formula (A) in which n=2.

The palladium salt is selected preferably from the group comprisingpalladium carboxylates of the formula ("B"): (R₁ COO)₂ Pd, the allylcomplexes of palladium having a carboxylate radical of the formula("C"): (R₂ PdR₁ COO)₂, and the allyl complexes of palladium having theformula ("D"); R₂ PdOR₁ in which:

R₁ represents a radical selected from the group comprising alkylradicals having from about 1 to 6 carbon atoms, such as the methyl,ethyl, isopropyl, and n-butyl radicals and aryl radicals, such as thephenyl, tolyl, benzyl and naphthyl radicals, these radicals beingoptionally substituted.

R₂ represents a radical of the formula: ##STR3## in which R₃ representsa hydrogen atom or the radical R₁.

As examples of palladium carboxylates of formula ("B") which can be usedin the process of the invention, mention may be made of palladiumacetate and palladium benzoate.

As examples of allyl complexes of palladium of formula ("C") which canbe used in the process of the invention, mention may be made of thecompounds of the following structures: ##STR4##

As example of complex of formula ("D") one may mention the compound ofthe formula: ##STR5##

The solvent is selected preferably from the group of aprotic solventscomprising dimethylformamide, hexamethylphosforus triamide,dimethylacetamide and N-methylpyrrolidone.

The carboxylic acid optionally used in the process of the presentinvention has the general formula R₄ COOH, in which R₄ represents aradical selected from among the group comprising the alkyl and arylradicals, optionally substituted.

In accordance with one particular embodiment of the process of theinvention, there is employed a carboxylic acid of the formula R₄ COOH,in which R₄ represents an acrylic or cyclic alkyl radical having fromabout 1 to 12 carbon atoms. Mention may be made in particular of theacids of the following formulae: ##STR6##

In accordance with another specific embodiment of the process there maybe employed a carboxylic acid of the formula R₄ COOH in which R₄represents a radical having a formula selected from the group comprisingof: ##STR7## in which R₅ represents a radical selected from the groupcomprising hydrogen, OH, and the alkyl radicals having from about 1 to12 carbon atoms.

Mention may be made in particular of the acids of the followingstructural formulae: ##STR8##

In the process of the invention a temperature between about -5° C. andabout +150° C. is generally employed. The temperature is preferablyselected from between about 10° C. and 35° C. when operating without theaddition of a carboxylic acid. When operating in the presence of thelatter, the temperature is preferably between about 50° C. and 100° C.

The use of a carboxylic acid, which increases the stability of thecatalyst system, makes it possible to carry out the reaction at a highertemperature. This results in an increase in the reaction velocity and,therefore, an increase in the yield of the desired alcohol.

The molar ratio of butadiene to water employed in the process ispreferably between about 0.1 and 10:1. More particularly, it ispreferred to use the butadiene and the water in a molar ratio close toabout 1:1. The ratio of the number of mols of butadiene to the number ofgram-atoms of palladium is generally between about 100 and about 1000to 1. A value of close to 300:1 is preferred. Values less than orgreater than this range are not excluded since they do not affect theselectivity, but only the reaction velocity. In order to obtain the bestselectivity, one preferably operates with a molar ratio of water toboric acid, B(OH)₃, of between about 0.1 and about 20:1. Even morepreferably, there is used a molar ratio of H₂ O to B(OH)₃ of betweenabout 2 and about 10:1.

The ratio of the number of mols of carboxylic acid to the number ofgram-atoms of palladium is preferably between about 0.5 and about 20:1.Even more preferably it is between about 2 and about 6:1.

It is preferred to carry out the process of the invention in ahomogeneous medium. The boric acid will therefore be used in an amountwhich does not exceed the limit of solubility (250 g/l of solventapproximately at room temperature). The amounts of boric acid aretherefore determined by the amounts of solvent. The latter must besufficient for the butadiene to be soluble in the water-solvent mixture.

The process of the invention is desirably conducted at autogenouspressure, although pressures greater or less than autogenous pressureare not excluded from the invention.

The reaction time, when operating within the above-indicated preferredtemperature ranges, is preferably between about 1 and 30 hours. Beyond30 hours, the formation of heavy compounds increases.

In order to decrease the formation of heavy compounds (oligomers ofbutadiene, non-functional polymers and polymers having alcoholfunctions) one may add a phosphine, such as triphenylphosphine, P(φ)₃,to the reaction system. A phosphine is preferably used in an amount suchthat the atomic ratio: P3+/Pd--is between about 0.1 and about 0.5:1.This ratio is preferably close to about 0.25:1.

The process of the invention can be carried out continuously orbatchwise. The products obtained having the formula ("A") can behydrogenated to form saturated linear alcohols of the following formula:##STR9## where n=2 or 4 as in formula ("A") above. This can be done byhydrogenation at a pressure of 50 bars of hydrogen employing pentane asthe solvent at a temperature of about 20° C., employing a catalyst ofpalladium or platinum deposited on carbon black support in the amount of10% of palladium or platinum. Alternatively, said products may beisomerized and hydrogenated to form saturated linear alcohols of theformula: ##STR10## where n has the same meaning. This can be done byisomerizing the product of formula ("A") in dioxane as a solvent at atemperature of about 100° C. over a catalyst of palladium,acetylacetonate and triphenylphosphine and then hydrogenated as above toproduce saturated linear alcohols of the above formula.

These saturated linear alcohols are precursors of biodegradabledetergents, which can be prepared by reaction of the alcohol withethylene oxide at a temperature of about 140° C. to provide a non-ionicdetergent. Those saturated alchohols having a formula RCH₂ OH can alsobe converted to ionic detergents by reaction with sulfuric chlorohydride(HCl-SO₃) to produce compounds of the formula RCH₂ --O--SO₃ H which canbe neutralized with a base, such as ammonia, to produce an ionicdetergent of the formula RCH₂ --O--SO₃ NH₄.

The compounds of formula "A" can also be isomerized to form ketones ofthe following formula: ##STR11## or isomerized and hydrogenated to formketones of the following formula: ##STR12## In both of these formulae,n=2 or 4. This can be done by isomerizing the compound of formula "A" ata temperature of about 110° C. over a catalyst of palladium or platinumon a carbon black support or a catalyst of hydridochlorotris(triphenylphosphine) ruthenium. Similarly, the products of formula "A"can be subjected to this same isomerization as just described and thenhydrogenated as described above for the production of saturated linearalcohols.

The process of the invention is preferably, but not necessarily, carriedout in an oxygen-free atmosphere.

SPECIFIC DESCRIPTION OF THE INVENTION

In order to disclose more clearly the nature of the present invention,the following examples illustrating the invention are given. It shouldbe understood, however, that this is done solely by way of example andis intended neither to delineate the scope of the invention nor limitthe ambit of the appended claims. In the examples which follow, andthroughout the specification, the quantities of material are expressedin terms of parts by weight, unless otherwise specified.

EXAMPLES 1 TO 8

80 mg. of palladium acetate (0.35 mg. atom of Pd) and 1 g. (16millimols) of boric acid were introduced into a thick-walled glass tubeand agitated by a Teflon-coated bar, driven by a magnetic agitator. Thetube was purged three times by a vacuum-argon system and thereupon 10 g.of dimethylformamide, the amount of water indicated in Table I, below,and 4.5 g. of butadiene (92 millimols) were added one after the other.

Agitation of the contents was effected for 24 hours at 20° C. Analysisby gaseous-phase chromatography showed that the following four products(I to IV) were obtained: ##STR13##

(III) oligomerization products of butadiene; and

(IV) polymerization products of butadiene having more than 24 carbonatoms.

These compounds can be separated from each other by any techniquewell-known to the man skilled in the art, such as, for instance,distillation under reduced pressure.

The results obtained are given in Table I, below.

In a number of the examples which follow and in a number of the tableswhich follow, the products obtained will be referred to by Nos. I, II,III and IV, which will be employed to indicate the products asidentified by the same numbers above.

EXAMPLES 9 TO 14

The same procedure of Example 1 was repeated, but varying amounts ofboric acid and water as indicated in Table II, below, were employed. Theresults obtained are indicated in Table II, below.

EXAMPLES 15 TO 18

The procedure of Example 1 was repeated, but increasing the amount ofsolvent (dimethylformamide) from 10 to 15 g. and using either 1 g. or 2g. of boric acid with variable amounts of water as indicated in TableIII, below. The results obtained are given in said Table III, below.

EXAMPLES 19 TO 22

The procedure of Example 1 was repeated, but with a molar ratio of H₂ Oto B(OH)₃ of 4 and using the different catalysts indicated in Table IV,below, which table also sets forth the results obtained.

EXAMPLE 23

The procedure of Example 1 was repeated, but employing a molar ratio ofH₂ O to B(OH)₃ of 4 and adding 29.6 mg. of triphenylphosphine of theformula: ##STR14##

The conversion rate of the butadiene was 27.4%. There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.560 g.                                                      II              0.095 g.                                                      III             0.142 g.                                                      IV              0.323 g.                                                      ______________________________________                                    

EXAMPLE 24

The procedure of Example 23 was repeated, but adding, instead oftriphenylphosphine, 57.8 g. of metasulfonated triphenylphosphine of theformula: ##STR15##

The conversion rate of the butadiene was 34.2%

There was obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.629 g.                                                      II              0.149 g.                                                      III             0.161 g.                                                      IV              0.400 g.                                                      ______________________________________                                    

EXAMPLES 25-27

The procedure of Example 1 was repeated, but with a ratio of H₂ O toB(OH)₃ of 4, but varying the nature of the solvent (in each case 10 g.of solvent was used). The solvents employed and results obtained are setforth in Table V, below.

EXAMPLES 28 TO 34

The procedure of Example 1 was repeated, but with a molar ratio of H₂ Oto B(OH)₃ of 4, and also varying the amount of palladium acetate. Theresults are set forth in Table VI, below.

EXAMPLES 35 TO 37

The procedure of Example 1 was repeated, but with a molar ratio of H₂ Oto B(OH)₃ of 4, and also varying the temperatures. The results are setforth in Table VII, below.

EXAMPLES 38 TO 40

The procedure of Example 1 was repeated, but with a molar ratio of H₂ Oto B(OH)₃ of 4, and also varying the butadiene concentrations. Theresults are set forth in Table VIII, below.

EXAMPLES 41 TO 50

The procedure of Example 1 was repeated, but using a molar ratio of H₂ Oto B(OH)₃ of 2 (Table IX, below, for Examples 41 to 45) or else 4 (TableX, below, for Examples 46 to 50) and varying the reaction times. Theresults are shown in Tables IX and X, below.

EXAMPLE 51

1.20 g. (5.34 milligram atoms of Pd) of palladium acetate and 15 g. (242millimols) of orthoboric acid were introduced into an 0.5 literstainless steel autoclave. It was purged three times by a vacuum-argonsystem and 164 g. of dimethylformamide, 17.64 g. of water (0.98 mol) and62 g. of butadiene (1.15 mol) were then added one after the other.Agitation was effected at 20° C. for 24 hours. The conversion rate ofthe butadiene was 41%. After addition of water and neutralization of theboric acid by sodium bicarbonate, 27 g. of organic phase were obtained,analysis of which by gaseous-phase chromatography shows that itcontains:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               10.08 g.                                                      II                 3 g.                                                       III              1.31 g.                                                      IV              11.29 g.                                                      ______________________________________                                    

EXAMPLES 52 TO 58

80 mg. of palladium acetate (0.35 milligram atom of Pd), 1 g. (16millimols) of orthoboric acid and an amount of carboxylic acid, suchthat the atomic ratio H+/Pd was equal to 2, were added to a thick-walledglass tube which was stirred by a Teflon-coated bar driven by a magneticagitator. The tube was purged three times by a vacuum-argon system andthereupon there were introduced, in succession, 10 g. ofdimethylformamide, 1.2 g. of water (molar ratio H₂ O/B(OH)₃ =4) and 4.5g. of butadiene (92 millimols).

Agitation was effected for 24 hours at 25° C.

The results obtained are indicated in Tables XI and XIA, below.

EXAMPLE 59

The procedure of Example 1 was repeated, but employing:

Pd (φCOO)₂ =0.136 g. (0.36 milligram atom of Pd)

B(OH)₃ =1 g.

dimethylformamide=9.3 g.

H₂ O=1.18 g.

butadiene=4.6 g.

Heating was effected at 50° C. for 2 hours.

The conversion rate of the butadiene was 37.7%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.807 g.                                                      II              0.267 g.                                                      III             0.139 g.                                                      IV              0.501 g.                                                      ______________________________________                                    

EXAMPLE 60

The procedure of Example 59 was repeated, but with heating at 50° C. for16 hours.

The conversion rate of the butadiene was 63.5%. There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.140 g.                                                      II              0.333 g.                                                      III             0.239 g.                                                      IV              0.866 g.                                                      ______________________________________                                    

EXAMPLE 61

The procedure of Example 60 was repeated, but using 1.79 g. of H₂ O.

The conversion rate of the butadiene was 54.8%. There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.325 g.                                                      II              0.296 g.                                                      III             0.240 g.                                                      IV              0.305 g.                                                      ______________________________________                                    

EXAMPLE 62

The procedure of Example 1 was repeated, but employing:

Pd(AcO)₂ =81.6 mg. (0.36 milligram atom of Pd)

benzoic acid=88 mg. (0.72 millimol)

B(OH)₃ =1 g.

dimethylformamide=9.6 g.

H₂ O=1.23 g.

butadiene=4.7 g.

Heating was effected at 50° C. for 2 hours.

The conversion rate of the butadiene was 34%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.815 g.                                                      II              0.206 g.                                                      III             0.186 g.                                                      IV              0.335 g.                                                      ______________________________________                                    

EXAMPLE 63

The procedure of Example 62 was repeated, but using 1.78 g. of H₂ O.

The conversion rate of the butadiene was 21.3%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.506 g.                                                      II              0.111 g.                                                      III             0.162 g.                                                      IV              0.149 g.                                                      ______________________________________                                    

EXAMPLE 64

Into a 125 ml. stainless steel autoclave there were introduced:

Pd(AcO)₂ =0.238 g. (1.06 milligram atom of Pd)

benzoic acid=0.263 g. (2.15 millimols)

B(OH)₃ =3 g.

dimethylformamide=28.5 g.

H₂ O=3.6 g.

butadiene=16 g.

Heating was effected with agitation at 65° C. for 1 hour.

The conversion rate of the butadiene was 30.4%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               2.292 g.                                                      II              0.693 g.                                                      III             0.714 g.                                                      IV              0.918 g.                                                      ______________________________________                                    

EXAMPLE 65

The procedure of Example 1 was repeated, but using:

Pd(AcO)₂ =0.080 g. (0.35 milligram atom of Pd)

benzoic acid=0.187 g. (1.53 millimols)

B(OH)₃ =1 g.

dimethylformamide=9.7 g.

H₂ O=1.20 g.

butadiene=4.6 g.

Heating was effected at 50° C. for 4 hours.

The conversion rate of the butadiene was 25.8%

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.702 g.                                                      II              0.118 g.                                                      III             0.159 g.                                                      IV              0.156 g.                                                      ______________________________________                                    

EXAMPLE 66

The procedure of Example 65 was repeated, but heating at 50° C. for 16hours.

The conversion rate of the butadiene was 55.6%. There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.333 g.                                                      II              0.167 g.                                                      III             0.286 g.                                                      IV              0.393 g.                                                      ______________________________________                                    

EXAMPLE 67

The procedure of Example 66 was repeated, but using 1.8 g. of H₂ O.

The conversion rate of the butadiene was 35%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.921 g.                                                      II               0.08 g.                                                      III             0.161 g.                                                      IV               0.0 g.                                                       ______________________________________                                    

EXAMPLE 68

The procedure of Example 67 was repeated, but heating at 65° C. for 2hours.

The conversion rate of the butadiene was 29.1%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               0.757 g.                                                      II              0.110 g.                                                      III             0.193 g.                                                      IV              0.035 g.                                                      ______________________________________                                    

EXAMPLE 69

The procedure of Example 64 was repeated, but using:

Pd(AcO)₂ =0.162 g. (0.724 milligram atom of Pd)

benzoic acid=0.361 g. (2.96 millimols)

B(OH)₃ =2 g.

dimethylformamide=19 g.

H₂ O=3.6 g.

butadiene=10 g.

Heating was effected at 80° C. for 1 hour.

The conversion rate of the butadiene was 31.4%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.59  g.                                                      II              0.254 g.                                                      III             0.572 g.                                                      IV              0.230 g.                                                      ______________________________________                                    

EXAMPLE 70

The procedure of Example 69 was repeated, but using 0.110 g. ofpalladium acetate (0.49 milligram atom of Pd) and 0.243 g. of benzoicacid (2 millimols).

The conversion rate of the butadiene was 27.1%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.196 g.                                                      II              0.190 g.                                                      III             0.335 g.                                                      IV              0.097 g.                                                      ______________________________________                                    

EXAMPLE 71

The procedure of Example 64 was repeated, but using:

Pd(AcO)₂ =0.166 g. (0.74 milligram atom of Pd)

benzoic acid=0.361 g. (2.96 millimols)

B(OH)₃ =4 g.

dimethylformamide=28.5 g.

H₂ O=7 g.

butadiene=11 g.

Heating was effected with agitation at 95° C. for 30 minutes.

The conversion rate of the butadiene was 44.1%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I               1.807 g.                                                      II              0.413 g.                                                      III             1.179 g.                                                      IV              0.413 g.                                                      ______________________________________                                    

EXAMPLE 72

The procedure of Example 71 was repeated, but using 0.152 g. ofpalladium acetate (0.68 milligram atom of Pd), 0.334 g. of benzoic acid(2.73 millimols) and 14 g. of butadiene.

Heating was effected at 80° C. for 1 hour.

The conversion rate of the butadiene was 29.1%.

There were obtained:

    ______________________________________                                        Compound No.    Amount                                                        ______________________________________                                        I                2.06 g.                                                      II              0.242 g.                                                      III             0.643 g.                                                      IV              0.428 g.                                                      ______________________________________                                    

                                      TABLE I                                     __________________________________________________________________________    Amount           Conversion                                                   of water  Molar ratio                                                                          rate of Products obtained (g)                                Examples                                                                           (g)  H.sub.2 O/B(OH).sub.3                                                                butadiene (%)                                                                         I   II  III IV                                       __________________________________________________________________________    1    0    0      3.5     0   0   0.1 0                                        2    0.14 0.48   11.5    0.230                                                                             0.058                                                                             0.079                                                                             0.112                                    3    0.29 1      30.3    0.481                                                                             0.2 0.095                                                                             0.605                                    4    0.62 2.1    34.9    0.413                                                                             0.22                                                                              0.113                                                                             0.875                                    5    1.09 3.65   34      0.572                                                                             0.22                                                                              0.084                                                                             0.668                                    6    1.2  4.2    31.9    0.514                                                                             0.157                                                                             0.081                                                                             0.64                                     7    1.85 6.5    28.7    0.573                                                                             0.133                                                                             0.130                                                                             0.49                                     8    2.8  9.45   21      0.397                                                                             0.13                                                                              0.119                                                                             0.24                                     __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________               Amount      Conversion                                             Amount of  of water                                                                           Molar ratio                                                                          rate of Products obtained (g)                          Examples                                                                           B(OH).sub.3 (g)                                                                     (g)  H.sub.2 O/B(OH).sub.3                                                                butadiene (%)                                                                         I   II  III                                                                              IV                                  __________________________________________________________________________     9   0     0    0      0       0   0   0  0                                   10   0.5   0.3  2.04   32      0.192                                                                             0.150                                                                             0.10                                                                             1                                   11   1.01  0.55 1.86   46.7    0.832                                                                             0.268                                                                             0.10                                                                             1.05                                12   2.01  1.34 2.28   23      0.695                                                                             0.160                                                                             0.02                                                                             0.30                                13   2.09  2.36 3.9    15.4    0.36                                                                              0.091                                                                             0.12                                                                             0.246                               14   1.96  3.43 6      15.9    0.358                                                                             0.018                                                                             0.08                                                                             0.17                                __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________                            Conversion                                            Amount of  Amount of                                                                           Molar ratio                                                                          rate of Products obtained (g)                         Examples                                                                           B(OH).sub.3 (g)                                                                     H.sub.2 O (g)                                                                       H.sub.2 O/B(OH).sub.3                                                                butadiene (%)                                                                         I  II III                                                                              IV                                   __________________________________________________________________________    15   1     1.1   3.7    25      0.197                                                                            0.06                                                                             0.026                                                                            0.757                                16   1     1.67  5.5    35.7    0.612                                                                            0.164                                                                            0.056                                                                            0.680                                17   2     2.49  4.2    21.8    0.533                                                                            0.136                                                                            0.029                                                                            0.330                                18   2     3.73  6.7    22.7    0.663                                                                            0.090                                                                            0.088                                                                            0.266                                __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    Catalyst           Number of                                                                           Conversion                                                         Amount                                                                             milli-gram                                                                          rate of                                                                              Products obtained (g)                         Example                                                                            Nature   (g)  atoms of Pd                                                                         butadiene %                                                                          I  II III                                                                              IV                                   __________________________________________________________________________    19   Pd(CH.sub.3COO).sub.2                                                                  0.08 0.35  47.0   0.897                                                                            0.271                                                                            0.090                                                                            0.944                                20   1        0.107                                                                              0.4   55     0.392                                                                            0.264                                                                            0.037                                                                            1.48                                 21   2        0.063                                                                              0.306 27.8   0.486                                                                            0.130                                                                            0.024                                                                            1.10                                 22   (φ-COO).sub.2 Pd                                                                   0.121                                                                              0.325 37.2   0.943                                                                            0.221                                                                            0.094                                                                            0.419                                __________________________________________________________________________     ##STR16##                                                                     2 (CH.sub.3COO Pd C.sub.3 H.sub.5).sub.2 bis(π-allyl palladium acetate

                  TABLE V                                                         ______________________________________                                                      Conversion                                                      Nature of     rate of    Products obtained (g)                                Example                                                                              solvent    butadiene %                                                                              I    II   III  IV                                ______________________________________                                        25     Dimethyl-  47         0.897                                                                              0.271                                                                              0.090                                                                              0.944                                    formamide                                                              26     N--methyl- 27.4       0.522                                                                              0.101                                                                              0.104                                                                              0.408                                    pyrrolidone                                                            27     propyl     5          0.028                                                                              0.045                                                                              0.010                                                                              0.355                                    carbonate                                                              ______________________________________                                    

                                      TABLE VI                                    __________________________________________________________________________                         Number of                                                                           Conversion                                         Concentration                                                                              Amount of Pd                                                                          milligram-                                                                          rate of Products obtained (g)                      Example                                                                            of Pd (ppm)                                                                           acetate (mg)                                                                          atoms of Pd                                                                         butadiene (%)                                                                         I  II III                                                                              IV                                __________________________________________________________________________    28    760    26.5    0.118 10.7    0.230                                                                            0.045                                                                            0.018                                                                            0.175                             29   1320    46.5    0.207 23.4    0.456                                                                            0.116                                                                            0.046                                                                            0.39                              30   2250    79.5    0.35  47      0.897                                                                            0.271                                                                            0.090                                                                            0.944                             31   3000    105.6   0.470 58.3    1.034                                                                            0.343                                                                            0.139                                                                            1.164                             32   4000    140.8   0.627 68.3    1.198                                                                            0.414                                                                            0.192                                                                            1.315                             33   4500    158     0.705 74.4    1.159                                                                            0.468                                                                            0.212                                                                            1.414                             34   5070    180     0.800 77.2    1.216                                                                            0.468                                                                            0.253                                                                            1.653                             __________________________________________________________________________

                  TABLE VII                                                       ______________________________________                                                      Conversion                                                                    rate of                                                         Temperature   butadiene  Products obtained (g)                                Example                                                                              (°C.)                                                                             (%)        I    II   III  IV                                ______________________________________                                        35     10         11         0.139                                                                              0.036                                                                              0.020                                                                              0.315                             36     35         63.2       1.089                                                                              0.354                                                                              0.231                                                                              1.263                             37     50         66.6       0.771                                                                              0.419                                                                              0.323                                                                              1.491                             ______________________________________                                    

                  TABLE VIII                                                      ______________________________________                                        Amount of                                                                     butadiene     Conversion Products obtained (g)                                Example (g)       rate (%)   I    II   III  IV                                ______________________________________                                        38      2.48      36.8       0.592                                                                              0.151                                                                              0.080                                                                              0.450                             39      4.5       31.9       0.514                                                                              0.157                                                                              0.081                                                                              0.638                             40      9.65      12.6       0.500                                                                              0.150                                                                              0.077                                                                              0.520                             ______________________________________                                    

                  TABLE IX                                                        ______________________________________                                                      Conversion                                                                    rate of                                                         Reaction time butadiene Products obtained (g)                                 Examples                                                                             (hours)    (%)       I    II   III  IV                                 ______________________________________                                        41      5         13.2      0.235                                                                              0.090                                                                              0.043                                                                              0.38                               42      7         25.9      0.351                                                                              0.154                                                                              0.055                                                                              0.48                               43     17         39        0.972                                                                              0.220                                                                              0.083                                                                              0.56                               44     41         51        0.665                                                                              0.254                                                                              0.110                                                                               0.823                             45     95         54.7      0.405                                                                              0.364                                                                              0.130                                                                              1.56                               ______________________________________                                    

                  TABLE X                                                         ______________________________________                                        Reaction     Conversion                                                       time         rate of     Products obtained (g)                                Examples                                                                              (hours)  butadiene (%)                                                                             I    II   III  IV                                ______________________________________                                        46       7       12.6        0.23 0.075                                                                              0.030                                                                              0.260                             47      16       26.5        0.47 0.140                                                                              0.050                                                                              0.520                             48      24       31.9        0.51 0.157                                                                              0.081                                                                              0.638                             49      40       43          0.833                                                                              0.310                                                                              0.170                                                                              0.960                             50      96       48.7        0.861                                                                              0.340                                                                              0.200                                                                              1.050                             ______________________________________                                    

                  TABLE XI                                                        ______________________________________                                                             Con-                                                                          version                                                                       rate                                                     Ex-  Acid Added      of bu-                                                   am-              weight  tadiene                                                                             Products obtained (g)                          ples type        (mg)    (%)   I    II   III  IV                              ______________________________________                                        52                                                                                  ##STR17##  87.2    27.4  0.679                                                                              0.124                                                                              0.074                                                                              0.31                            53                                                                                  ##STR18##  98      30    0.684                                                                              0.150                                                                              0.103                                                                              0.228                           54                                                                                  ##STR19##  95      25.2  0.636                                                                              0.098                                                                              0.052                                                                              0.333                           55                                                                                  ##STR20##  94      31.1  0.770                                                                              0.159                                                                              0.074                                                                              0.453                           ______________________________________                                    

                  TABLE XIA                                                       ______________________________________                                                              Con-                                                                          ver-                                                                          sion                                                                          rate                                                                          of                                                      Ex-  Acid added       buta-                                                   am-               weight  diene                                                                              Products obtained (g)                          ples type         (mg)    (%)  I    II   III  IV                              ______________________________________                                        56                                                                                  ##STR21##   130     11   0.266                                                                              0.029                                                                              0.075                                                                              0.069                           57                                                                                  ##STR22##   93      32.3 0.705                                                                              0.200                                                                              0.151                                                                              0.491                           58                                                                                  ##STR23##   82      29.5 0.535                                                                              0.103                                                                              0.081                                                                              0.595                           ______________________________________                                    

The terms and expressions which have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theinvention claimed.

What is claimed is:
 1. An unsaturated fatty alcohol of the formula:##STR24## in which n=2 or
 4. 2. Hexadeca-1,6,10,15-tetraene-3-ol. 3.Tetracosa-1,6,10,14,18,23-hexaene-3-ol.